Bis-(triazolyl)-azo dyes



United States PatentO BIS-(TRIAZOLYD-AZO DYES Randolph Norris Shreve, West Lafayette, Ind., and Robert Koridon Charlesworth, Walnut Creek, Calif., assignors, by mesne assignments, to Research Corporation, New York, N. Y., a corporation of New York No Drawing. Application August 9, 1954 Serial No. 448,756

3 Claims. (Cl. 260-157) wherein n is an integer from zero to twelve, inclusive, and wherein R and R are the residues of substituted aryl radicals capable of coupling.

It is a primary object of the present invention to pro vide a novel series of dyestuffs. Another object of the present invention is to provide a novel series of dyestuffs which have active hydrogen atoms capable of forming a mordant. Still another object of the present invention is to provide a novel series of dyestuffs having applicability to a large variety of fabrics. Further, it is an object of the present invention to provide a series of dyestuffs having a wide variation of colors which may be applied to most fabrics by conventional dyeing techniques. Other objects will become apparent hereinafter.

In a copending application, Serial 396,344, filed December 4, 1953, now U. S. Patent 2,744,116, of which this application is a continuation-in-part, there is described a novel group of bis-triazolyl alkanes having the following structure: 7

wherein n is an integer from zero to twelve, inclusive.

The process of the present invention comprises the reaction of this novel intermediate material with coupling agents to form the dyestuffs of the present invention. Representative coupling materials which are suitable in the process of the present invention, include, for example, 3-methyl-l-phenyl-S-pyrazolone, -Kochs acid, Chicago acid, ortho-nitrophenol, salicylic acid, R and G acid, alphaand beta-naphthol, meta-phenylenediaminesulfonic acid, crocein, Laurents acid, Neville and Winthers acid,'dimethylaniline, barbituric acid, hydroquinone,

2,863,859 Patented 9, 1958 art and with the aid of the foregoing list will be apparent to those skilled in the art.

The reaction is usually accomplished by dissolving'the bis-triazolyl intermediate in an acid solution and cooling this solution to a temperature below that at which the bis-triazolyl salt material crystallizes from solution. This temperature will usually be below about twenty degrees centigrade, and probably about ten degrees centigrade, depending upon the particular concentration of the acid employed. Thus, concentrations between about two and about thirty percent of acid are satisfactory, usually, a ten percent acid solution is used. Various acids are suitable, including, for example, sulfuric, nitric, hydrochloric, sulfamic, acetic, et cetera, however, sulfuric acid is preferred because of its availability and non-interference in an aqueous solution with reaction components, the reaction, or the reaction products.

When this salt has precipitated, a solution of sodium nitrite is addedto the precipitated amine solution. Preferably, this sodium nitrite is added while cold, below about twenty degrees centigrade, usually about ten de grees centigrade. The concentration of the sodium nitrite may vary anywhere from one to thirty or forty percent,

however, a twenty percent solution is preferred. Normally, the sodium nitrite is employed in substantially twice the molar quantity-of sodium nitrite as the amine that is employed, since there are two reactive groups on the amine which are subject to diazotization. By stirring, or other agitation, while maintaining the reaction mixture cold, the solids will go into solution. This will signify an end of the reaction period, 'and usually takes between five and thirty minutes, depending on the degree of agitation, the temperature and the particular reactants.

After the diazotized salt has been prepared thecoupling agent is added to the solution. Preferably, the coupling agent is suspended in water, or a miscible organic solvent such that reaction can occur in the water, and the coupling solution is added relatively slowly to insure a substantially uniform reaction rate. The amount of coupling reagent which is employed is two molar times that of the bis-triazolyl amine which is originally employed, since there are two reactive groups on each of the bis-triazolyl amine rnolecules. The molar quantity of the coupling agent will be substantially the same as the molar quantity of the sodium nitrite which is employed. However, it is to be understood that excesses of the sodium nitrite or coupling agent may be employed without seriously hindering the results. 7

The period for addition of the coupling agent will depend on the amount of reaction components, the degree of reaction time involved, and the reaction products which are prepared. Generally speaking, the dye thusprepared will precipitatefrom the reaction mixture, however, if it does not precipitate per so by adjustingthe pH in a conventional manner,- precipitation of the dye may be accomplished, by the addition of an organic solvent. Also, conventionally, by utilizing the alkaline H-acid test, it can be determined whether the reaction is substantially complete. r I i The dye thus-precipitated is separated by filtration, cen trifugation, or decantation, in conventional manner, and

recovered. v 7

Various testing procedures are available for determining the amount of pure dye in the dyestuif material thus-prepared are known in the art, however, we have found that results will vary from sixty percent and thetheoretical yield based on the bis-triazolyl amine employed as the starting material in the use of pure dyes.

After separation .of the pure dye, it can be dried and applied to fabrics in conventional manner, witli or without a mordant, as desired. The 'ac tivehydrogen atoms on the tria'zolyl center moiety aresubject to mordantingf The following examples are given to illustrate the process and products of the present invention, but are not to be construed as limiting.

Example 1 room temperature slowly. It was allowed to set at room temperature for twelve hours. The reddish-violet mixture is the coupled diazo compound of para-nitroaniline and H-acid, having the following structure:

NII2

HO S i After heating this material to eighty degrees centigradc, ten parts of thirty percent sodium hydroxide and four parts of anhydrous sodium carbonate was added. Complete solution occurred, this solution having a bright blue m Salt Solution was added a Suspension of Parts 0f color. The solution was then placed in an ice-bath and mela-phenyleflediamineslllfoflic acid in Parts of Watercooled to five degrees centigrade wtih stirring. To this This addition was carried out portionwise over a period Cooled solution was added a cold solution f a tetraof forty-five minutes. After stirring an additional fifteen i d i m prepared as follows; minutes, a negative test with alkaline H-acid was obtained, T d twemyiwo m d d h (222) parts of so the solution was filtered with suction and a Biichner 0 3 tetramethylene 5- i -1 2 4- i was i f n and dried at 55 degfefis centigladfl There Was solved in 35 parts of ten percent sulfuric acid and cooled thus Obtained thirteen P Corresponding to P with stirring to five degrees centigrade. The resulting cent of the theoretical yield based on the bis-triazolyl emmixture was treated with a twenty percent solution of ployed, of a dye having the following structure: 1.38 parts of sodium nitrite in water. All solids dis- H053 HNN .\---NH soin Hie: -N=N-C -{CHzh-i) C J-N=N N111 v AH: N NH:

Example 2 solved. The tetrazotized triazole was added over a thirty The process of Example 1 was repeated, except that 1.1 minute period drop 9 the.reaction.mlxture.on finer part of dimethylaniline in 25 parts of water containing Paper gave a i reactlon w1th alkalme i i four grams of sodium acetate was utilized as the coupling mlxmre contammg comptlund correipondmg to Us agent. The mixture was tested for completion of the re- 3 tetramethylene'bls'(s'ammo'lfzll'mflzole) coupled action with alkaline H-acid. There was thus obtained W? the compound abov? fffflmuhzed w then treated 1.0 part of pure dye representing 58.8 percent of the Wm partpf phenql m we i A (11.99 theoretical yield based on the bis triazole employed as of the green mixture failed to react with alkaline H-acid. starting material. The mixture was worked at five degrees centlgrade for Example 3 two hours and then allowed to come to room tempera ture with stirring. The mixture was allowed to stand for The Proc653 of Examples 1 and 2 was p y 40 twelve hours. It was then treated with 25 parts of p that Parts Of sall'cylk acid in y Parts Of thirty percent sodium hydroxide at 85 degrees centigrade Water conlaining five Parts of anhydrous Sodium carbonand fifteen parts of sodium chloride. The dye was preate was p y as the Coupling agent The micipitated with fifty percent sulfuric acid. This mixture n n f the reaction Was accomplished Without was separated by filtering in a Biichncr funnel and dried After filtration in aBiichner funnel, the residue was acidiat degrees entigrade, Ther a thu obtained a fied with fifty Percent Sulfuric acid- The resulting black powder containing 5.04 parts of pure dye corrcr Was fi and the residue dried at 55 gr sponding to 60.9 percent of the theoretical yield based on centigrade. There was thus obtained a yellow dyestutf the bis-triazole employed. This material had the forcontaining 1.05 parts of pure dye corresponding to 44.8 mula:

NH: HIE-WI? IfiI- lITH OH nou=uo o-(oHni-e o-N=N N=N -N0 HOgS- SO H percent of the theoretical yield based on the bis-triazole Example 5 employed.

Example 4 A mixture of 1.38 parts of para-nitroaniline in three parts of 37.5 percent concentrated hydrochloric acid in three parts of water was cooled with five parts of water and five parts of ice. The hydrochloride of the amine precipitated. When the temperature of the mixture had reached five degrees centigrade, 3.5 parts of a cold solution containing twenty percent sodium nitrite was added. After a few minutes, all solids had dissolved and tests with Congo red and starch iodide paper indicated complete diazotization. To the resulting solution was added over a 45-minute period a solution of 3.41 parts (0.01 mole) of H-acid in 25 parts of water containing 0.55 part anhydrous sodium carbonate. After ten minutes a drop of the reaction mixture failed to react with alkaline H-acid. The mixture was worked at five degrees centigrade for two and one-half hours, and then allowed to come to In a manner similar to that of Example 4, para-chloroaniline was coupled with H-acid in anhydrous sodium carbonate. The blue solution which resulted after partial purification was cooled to five degrees Centigrade with stirring over a thirty minute period, 0.01 mole of tetrazotized bis-triazole prepared as indicated above was added thereto. At the end of thirty minutes a spot of the red mixture gave a faint coloration with alkaline H-acid on filter paper. To the mixture was added 0.94 gram (0.1 mole) of phenol and ten milliliters of water. After ten minutes, a negative test with H-acid was obtained. The mixture was worked for 2.5 hours at five degrees centigrade and allowed to come to room temperature with stirring. It was set aside for twelve hours and then heated to degrees centigrade. The hot mixture was treated with 25 milliliters of thirty percent sodium hydroxide and fifteen grams of sodium chloride. The dye was then precipitated with fifty percent sulfuric acid. Filtration was ac- .aseasee 5 complished in a Biichner tunnel to yield a black dyestuif, which, when dried at 55 degrees centigrade, contained 3.35 grams of pure dye corresponding to a 41 percent yield of the theoretical, based on the bis-triazole. This material has the formula:

HO MJ.

Example 6 In a manner similar to the foregoing examples, the following bis-azo dyes were prepared, utilizing the histriazolyl amine alkane as described above. In this case, for the purposes of convenience, the following chart recites those compounds prepared wherein the carbon chain between the triazolyl groups contains four carbon atoms:

1 Sodium acetate bufiered.

The conditions referred to therein refer to the actual hydrogen ion concentration of the solution in which the coupling occurred. The column listed Color is the final color of the dis-azo dye prepared from the reagent specified under the condition specified.

r on either the color or the color fastness of the dye.

ene, octamethylene, nonamethylene, decamethylene, et cetera, as well as the bis-(5-amino-1,2,4-triazolyl). Additionally, it is to be understood that other coupling agents may be substituted for those of the examples.

By a proper selection of the coupling agents used to make the final dye, the color of the above dyes may be varied from red to violet, that is, across the whole of the visible spectrum. Certain varying color eifects will also be accomplished by a proper selection of the reaction media employed, that is, whether it is basic, acidic, or neutral, or the particular pH employed.

The color fastness to light, to crocking, to laundering, to perspiration, et cetera, of the dyes of the present invention is comparable to the benzidine dyes. In general, the after-treatment with copper sulfate increases the color fastness of the dyes to light, crocking, laundering and perspiration. Of course, other metals than copper may be used as mordanting materials, and will have an effect on the color fastness. Apparently, the chain length of the alkylene bridge of the intermediate has little effect The tris-azo and dis-azo dyes can be applied to Vicara (Virginia-Carolina Chemical Corporationa synthetic fiber made from corn protein. erties and is used principally in blends with wool.), nylon, wool, cotton, viscose, rayon and silk with very satisfactory results.

Various modifications may be made in the present invention without departing from the spirit or scope thereof and it is to be understood that we limit ourselves only as defined in the appended claims.

We claim: Example 7 1. A dye having the formula The following chart illustrates certain tris-azo dyes prepared from the bis-triazole of adipic acid, that is, 3- w fi tetramethylene-bis-(5-amino-1,2,4-triazole), and wherein RN=NC d-(CHzh-O CN=NR' one coupling agent comprises a previously diazotized material. The preparation of the following tris-azo 'dyes was accomplished: wherem R and R' are coupling components.

Primary Secondary Secondary Primary Diazotized Amine Conditions Coupler Conditions Diizotized Conditions Coupler Color mine 1. p-Nitroaniline Acidic H-aeid Alkaline Bistriazolev Alkaline Phenol Green.

4- 2. alpha-Naphthylamine Acidic J'-acid Alkaline do Alkaline do Red.

4 3. p-Nitroaniline Acidic do..-- Alkaline -do Alkaline o-Nitrophenol..- Do.

4 4. Aniline Acidic H-acid Alkaline do Alkaline Phenol Violet.

-r 4- 5. p-Aminophenol Acidic .do Alkaline -do Alkaline do Blue.

4 6. p-Chloroaniline Acidic d0. Alkaline do Alkaline do Do.

2. A dye having the formula:

NH: t-t tt- OH HON= N-C o-(cHm-o CN=N N=N@NO;

It resembles wool in its prop- 3. A dyc having the formula:

References Cited in the file of: this patent UNTTED STATES PATENTS 2,346,531 Allen et al Apr. 11, 1944 2,432,419 Heimbach Dec. 9, 1947 2,490,967 Kaiser Dec. 13, 1949 2,671,775 Hanhart Mar. 9, 1954 2,744,116 Slneve et a1 May 1, 1956 FOREIGN PATENTS 173,521 Austria Dec. 27, 1952 

2. A DYE HAVING THE FORMULA: 